Chiral Chemistry (CC, Online ISSN 3106-8405) is an open-access quarterly journal dedicated to publication and dissemination of high-impact, original, and leading research in the field of chiral chemistry and technologies. The journal provides a platform for pioneering theoretical, experimental, and applied studies, promoting fundamental understanding, advancements, and applied innovations across a broad range of scientific and industrial applications.
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Chiral Chemistry (CC, Online ISSN 3106-8405) is an open-access quarterly journal dedicated to publication and dissemination of high-impact, original, and leading research in the field of chiral chemistry and technologies. The journal provides a platform for pioneering theoretical, experimental, and applied studies, promoting fundamental understanding, advancements, and applied innovations across a broad range of scientific and industrial applications.
more >
Precisely controlling the supramolecular chirality of polymer assemblies remains a persistent challenge. Herein, we report the synthesis of various main-chain chiral azopolyesters with side azobenzenegroups through the regioselctive ring-opening ...
Precisely controlling the supramolecular chirality of polymer assemblies remains a persistent challenge. Herein, we report the synthesis of various main-chain chiral azopolyesters with side azobenzenegroups through the regioselctive ring-opening copolymerization of cyclic anhydrides and enantiopure epoxides with different spacer lengths between the chiral stereocenter and the azobenzene chromophore. The influences of both the spacer length and main-chain backbone structure on the supramolecular chirality of the resulting azopolyester assemblies are investigated in detail. The slight change in main-chain structure or/and the flexible spacer allows successful control over chiral consistency or chirality inversion in the assemblies, leading to two distinct odd–even effects. This effect is also reflected in the liquid crystalline properties of the azopolyesters. These findings provide a novel strategy for modulating supramolecular chirality in polymer assemblies.
Axially chiral biaryls exhibit broad applications across diverse disciplines, and thus the development of conceptually new methods for accessing this structural motif remains highly desirable. Herein, we report the successful implementation of atroposelective ...
Axially chiral biaryls exhibit broad applications across diverse disciplines, and thus the development of conceptually new methods for accessing this structural motif remains highly desirable. Herein, we report the successful implementation of atroposelective de novo benzene formation via asymmetric [2+4] annulation in the enantioselective synthesis of axially chiral 1,2'-binaphthyls using β-substituted α-naphthylalkynes and o-iodostyrenes as C-4 and C-2 synthons, respectively. This nickel/PyrOX-catalyzed annulation reaction features a broad substrate scope (43 examples), excellent regiocontrol, exclusive 6-endo cyclization, and good to high enantioselectivity (up to 92% ee). Furthermore, the synthetic utility of the products is demonstrated through their efficient derivatizations into a range of potential bidentate ligands and bifunctional organocatalysts.
Due to the conformational rigidity, the bridged-cyclic chiral phosphorus compounds have been demonstrated to show enantioinducing ability generally superior to conformationally flexible chiral phosphorus compounds as ligands or organocatalysts in ...
Due to the conformational rigidity, the bridged-cyclic chiral phosphorus compounds have been demonstrated to show enantioinducing ability generally superior to conformationally flexible chiral phosphorus compounds as ligands or organocatalysts in catalytic asymmetric reactions. However, investigations into the bridged-cyclic chiral phosphorus compounds are relatively much rarer than the non-bridged-cyclic phosphorus compounds resulting from the paucity of efficient synthetic methods. In order to draw the attention of researchers who are interested in asymmetric synthesis and catalysis to this issue, in this review, we intend to summarize the progress in the synthesis of bridged-cyclic chiral phosphorus compounds and their applications in catalytic asymmetric reactions. We wish this review article could serve as a useful guide and stimulate, to some extent, the interests of asymmetric catalysis scholars to devote to this challenging but greatly important field.
Chiral nickel complexes of bis(oxazoline)s serve as highly active catalysts for an enantioselective reductive alkenylation of N-sulfonyl and N-sulfamoyl aldimines, using readily available alkenyl ...
Chiral nickel complexes of bis(oxazoline)s serve as highly active catalysts for an enantioselective reductive alkenylation of N-sulfonyl and N-sulfamoyl aldimines, using readily available alkenyl bromides and triflates as reagents. The new method is readily scalable with low loadings of nickel catalysts, as low as 0.2 mol%. The reaction condition is almost neutral and tolerated polar groups of esters, thioethers, carbamates, heterocyclic pyridine and quinoline, and weakly acidic alcohols. Mechanistically, density functional theory (DFT) calculations reveal that alkenyl transfer to N-sulfonyl imines occurs on nickel catalysts via a classical 1,2-migratory insertion.
Amino acids are typical naturally occurring chiral compounds, whose enantiomeric pairs show distinct biological functions and markedly different application prospects. The precise chiral recognition of amino acid enantiomers is of great significance ...
Amino acids are typical naturally occurring chiral compounds, whose enantiomeric pairs show distinct biological functions and markedly different application prospects. The precise chiral recognition of amino acid enantiomers is of great significance in diverse fields including life sciences, medical diagnosis, and pharmaceutical development. Over the past decade, chiral fluorescent probes toward amino acids have gained considerable attention for enantiomer recognition. Among these probes, Schiff base chiral fluorescent probes have emerged as a powerful class of sensors for achieving high enantioselective recognition of amino acids, owing to their advantages of facile synthesis, tunable structure, facile functionalization, and excellent photophysical and coordination properties. This review systematically summarizes the research progress of such probes in the enantiomer recognition of different types of amino acids, including acidic, basic, non-polar, and polar amino acids. It focuses on discussing probe design strategies, enantioselective recognition, interaction mechanisms, and application developments. In addition, this paper also highlights and outlines the major challenges existing in this field and the difficult issues that need to be addressed in the future.
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated ...
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated in Rh-catalyzed asymmetric sulfonyl retentive S,N-difunctionalization of alkynyl N-sulfonylhydrazones with sulfenamides. The sulfonyl group or the corresponding sulfinic acid is retained in a formal migration. This mild and efficient protocol allows for straightforward construction of enantioenriched sulfonyl-based allylic sulfenamides with excellent chemo-, E/Z-, and enantioselectivity, thereby offering a creative strategy for achieving more atom-economic transformations of carbene precursors. Mechanistic studies reveal a three-step process involving S-allenylation, hydrosulfonylation, and an aza-Mislow-Evans rearrangement, with the hydrosulfonylation step governing enantioselectivity.
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product ...
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product synthesis. Denitrogenation demonstrates high activity and can engage in cyclization reactions with olefins, alkynes, carbon-heterocycles, aldehydes, and other reagents. This one-step operation enables the rapid construction of chiral heterocycles such as pyrroles and indoles, significantly shortening complex synthetic pathways. Innovations in chiral ligands, optimization of catalytic systems, and detailed studies on mechanisms have significantly enhanced the enantioselectivity and substrate applicability of denitrogenation reactions. This review highlights recent advancements in the synthesis of chiral heterocycles via denitrogenation reactions and systematically examines the reaction characteristics of various metal catalytic systems.
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction ...
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction of the related optically active organosilanes, organosulfides, organophosphine, and organochlorides. These compounds have shown considerable potential for preparing functional molecules and synthesizing natural products. Over the past few decades, considerable research efforts have focused on the design and development of transition-metal catalysts featuring chiral ligands for the asymmetric hydrogenation of such substrates. In parallel, in-depth mechanistic studies have been conducted to elucidate the pathways of these enantioselective hydrogenation reactions, significantly advancing the understanding of their catalytic behavior and stereocontrol. This review focuses on the recent momentum and key advancements in the enantioselective hydrogenation of vinyl silanes, vinyl sulfides, and vinyl chlorides. In addition, given the widespread industrial interest in these compounds, the practical utility of this transformation in the synthesis of chiral silanes, chiral thioethers, chiral alkyl chlorides, as well as related derivatives, is also discussed.
Transition metal-catalyzed asymmetric C–H activation is vital for chiral molecule synthesis but faces challenges in remote C–H functionalization due to traditional metallacycle constraints and difficulties in long-range chiral recognition. This review ...
Transition metal-catalyzed asymmetric C–H activation is vital for chiral molecule synthesis but faces challenges in remote C–H functionalization due to traditional metallacycle constraints and difficulties in long-range chiral recognition. This review summarizes three core strategies to address these issues: template-assisted chiral ligand control, norbornene-mediated palladium catalysis, and bifunctional catalyst control. These strategies achieve high enantioselectivity for diverse chiral architectures. Future directions include expanding to para-C–H bonds of arenes and aliphatic C–H bonds, developing robust chiral mediators/ligands, and applying the methodology to natural products and complex materials.
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent ...
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent advances in the catalytic asymmetric synthesis of chiral organogermanes, highlighting a shift from traditional resolution methods toward asymmetric catalytic approaches. The content is organized into three main categories: (i) synthesis of C-stereogenic germanes, (ii) synthesis of Ge-stereogenic germanes, and (iii) synthesis of other chiral germanes, including planar, inherent, and axially chiral types. Key synthetic methodologies are systematically examined, such as enantioselective alkene hydrofunctionalization, carbene insertion, coupling reactions, and [2+2+2] cycloaddition, utilizing a variety of catalytic systems ranging from transition metals (Rh, Cu, Ni, Co) and Lewis acids to engineered metalloenzymes. Particular emphasis is placed on the mechanistic insights and ligand design principles that enable stereochemical control in these transformations. We hope this review will inspire chemists working in related areas and contribute to the future advancement of this field.
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction ...
The asymmetric hydrogenation of vinyl silanes, vinyl sulfides, vinyl phosphines, and vinyl chlorides, those substituted with heteroatoms from the third-row of the periodic table, has emerged as a valuable and environmentally friendly method for the construction of the related optically active organosilanes, organosulfides, organophosphine, and organochlorides. These compounds have shown considerable potential for preparing functional molecules and synthesizing natural products. Over the past few decades, considerable research efforts have focused on the design and development of transition-metal catalysts featuring chiral ligands for the asymmetric hydrogenation of such substrates. In parallel, in-depth mechanistic studies have been conducted to elucidate the pathways of these enantioselective hydrogenation reactions, significantly advancing the understanding of their catalytic behavior and stereocontrol. This review focuses on the recent momentum and key advancements in the enantioselective hydrogenation of vinyl silanes, vinyl sulfides, and vinyl chlorides. In addition, given the widespread industrial interest in these compounds, the practical utility of this transformation in the synthesis of chiral silanes, chiral thioethers, chiral alkyl chlorides, as well as related derivatives, is also discussed.
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated ...
Sulfonylhydrazones are valuable carbene precursors in asymmetric synthesis; however, their use typically generates sulfinic acid, which is inevitably discarded as stoichiometric waste. In this work, the carbene chemistry and sulfur chemistry are integrated in Rh-catalyzed asymmetric sulfonyl retentive S,N-difunctionalization of alkynyl N-sulfonylhydrazones with sulfenamides. The sulfonyl group or the corresponding sulfinic acid is retained in a formal migration. This mild and efficient protocol allows for straightforward construction of enantioenriched sulfonyl-based allylic sulfenamides with excellent chemo-, E/Z-, and enantioselectivity, thereby offering a creative strategy for achieving more atom-economic transformations of carbene precursors. Mechanistic studies reveal a three-step process involving S-allenylation, hydrosulfonylation, and an aza-Mislow-Evans rearrangement, with the hydrosulfonylation step governing enantioselectivity.
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent ...
Chiral organogermanes hold great potential as bioisosteres in medicinal chemistry and functional materials, yet their development has long been hindered by a scarcity of efficient synthetic strategies. This review offers a comprehensive overview of recent advances in the catalytic asymmetric synthesis of chiral organogermanes, highlighting a shift from traditional resolution methods toward asymmetric catalytic approaches. The content is organized into three main categories: (i) synthesis of C-stereogenic germanes, (ii) synthesis of Ge-stereogenic germanes, and (iii) synthesis of other chiral germanes, including planar, inherent, and axially chiral types. Key synthetic methodologies are systematically examined, such as enantioselective alkene hydrofunctionalization, carbene insertion, coupling reactions, and [2+2+2] cycloaddition, utilizing a variety of catalytic systems ranging from transition metals (Rh, Cu, Ni, Co) and Lewis acids to engineered metalloenzymes. Particular emphasis is placed on the mechanistic insights and ligand design principles that enable stereochemical control in these transformations. We hope this review will inspire chemists working in related areas and contribute to the future advancement of this field.
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product ...
Over the past few decades, denitrogenation has proven to be an effective method for synthesizing high-value chiral heterocyclic compounds. These compounds find widespread applications in pharmaceutical chemistry, drug development, and natural product synthesis. Denitrogenation demonstrates high activity and can engage in cyclization reactions with olefins, alkynes, carbon-heterocycles, aldehydes, and other reagents. This one-step operation enables the rapid construction of chiral heterocycles such as pyrroles and indoles, significantly shortening complex synthetic pathways. Innovations in chiral ligands, optimization of catalytic systems, and detailed studies on mechanisms have significantly enhanced the enantioselectivity and substrate applicability of denitrogenation reactions. This review highlights recent advancements in the synthesis of chiral heterocycles via denitrogenation reactions and systematically examines the reaction characteristics of various metal catalytic systems.
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic ...
The synthesis of biaryl axially chiral amides and their derivatives—compounds that have shown promise as additives or catalysts in asymmetric catalysis—has traditionally relied on transition-metal catalysts. Herein, we report an NHC-catalyzed organocatalytic atropoenantioselective amidation between axially prochiral biaryl dialdehydes and amides that efficiently affords axially chiral imides. This method operates under metal-free and mild conditions, exhibits broad functional group tolerance and substrate scope, and delivers products with excellent enantioselectivities. Furthermore, a wide variety of axially chiral imides, amides, and related derivatives can be accessed through enantio-retentive transformations, offering a versatile and attractive strategy for their synthesis.
